JPH11256120A - Adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an adhesive composition usable for forming, a bond line for which the thickness and/or surface coverage can be determined by a means free from any unfavorableness, by including adhesive component(s) and light- emitting substance(s). SOLUTION: This adhesive composition is obtained by including one or more kinds of adhesive components in combination with one or more kinds of light- emitting substances, and pref. furthermore, fluorescent substance(s), luminescent substance(s) and phosphorescent substance(s), wherein the adhesive component(s) is suitably acrylic, cyanoacrylic, epoxy, polyurethane, silicone, cationic, hot-melt, and/or anaerobic adhesive(s), and the light-emitting substance(s) is pref. such one as to re-emit rays of light with wavelengths of about 200-700 nm, namely, ultraviolet to visible rays of light (e.g. distyrylbenzene), the content being normally about 0.001-1 wt.% based on the final composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to an adhesive composition suitable for bonding substrates together, especially when at least one of said substrates is optionally transparent. is there. In particular, the present invention provides a composition comprising at least one light emitting substance.

[0002]

BACKGROUND OF THE INVENTION In many applications, the bond line thickness of the adhesive between the substrates is a known non-uniform thickness. However, measuring the bond line thickness after the adhesive has hardened is very difficult without breaking the bond of the adhesive.

In certain applications, it is fundamental that not only the thickness of the adhesive bond can be measured, but also the degree of adhesive coating between the substrates. These factors have appreciable importance in the application, in which case the adhesive is used to coat the data-carrying layer, for example polycarbonate coated with a metallized reflective layer, with the desired transparent protective layer. A coupling line is formed between them. Failure to spread the adhesive will result in at least a non-flat thickness of the adhesive bonding between the data-bearing portions of the substrate surface and / or the substrate during retrieval of data from the selected substrate. Can be adversely affected.

[0004]

SUMMARY OF THE INVENTION An adhesive composition of the present invention comprising at least one light emitting material is provided for forming bond lines whose thickness and / or surface coverage can be analyzed in a defect-free manner. It has now been found that it can be used.

Therefore, in accordance with another aspect of the present invention, there is provided a defect-free method for measuring the adhesive bond line thickness between substrates, at least one of which is optionally transparent. You.

[0006]

DETAILED DESCRIPTION OF THE INVENTION Adhesive Composition An adhesive composition as defined herein refers to an adhesive composition comprising one or more adhesive components in combination with at least one light emitting material. . In addition to the adhesive composition of the present invention, a reactive diluent, a reinforcing material, a polymerization inhibitor,
Any of a number of additional materials, including, but not limited to, adhesion promoters and mixtures thereof, may be included. A two-component adhesive system as defined herein refers to a composition comprising at least one adhesive material and at least one hardener material, wherein the adhesive and hardener are separately packaged. . Hardener as defined herein means a chemical agent that can react with the adhesive to form a binding substance, optionally in the presence of a suitable catalyst, in combination with the adhesive. A one-component adhesive system, as defined herein, refers to an adhesive composition consisting of at least one adhesive material that may be present in combination with a hardener material. In some one-component adhesive compositions, the adhesive can be cured by the action of temperature, light, water, or by a free radical reaction to form a binding substance.
In such a system, it would not be necessary to include a chemical curing agent.

[0007] Adhesive materials suitable for use in the compositions of the present invention include the following groups: acrylic adhesives, cyanoacrylic adhesives, epoxy adhesives, polyurethane adhesives, silicone adhesives, cationic adhesives, hot adhesives. Includes melt adhesives, anaerobic adhesives and mixtures thereof. Suitable adhesive substances are described in the text under the heading "Adhesive substances"
In the section on the details.

Light Emitting Substance The adhesive composition of the present invention contains, as a basic feature, at least one light emitting substance. Light emitting material as defined herein means, in conventional expression, a material that absorbs and re-emits light. Preferred light emitting materials for use in the compositions of the present invention re-emit light in the wavelength range from about 200 nm to about 700 nm, ie, light from ultraviolet or visible light. Adhesive materials suitable for use in the adhesive compositions herein include fluorescent, luminescent, and phosphorescent materials.

[0009] Highly preferred adhesive compositions of the present invention include:
As a basic feature, it contains at least one fluorescent substance. Typically, suitable fluorescent materials for use in the present invention include:
A colorless or slightly colored organic compound that absorbs ultraviolet light (UV-light (e.g., daylight of 300-430 nm)) when in solution or applied to a substrate, and then absorbs 400 nm and 500 nm Re-emit most of the absorbed energy as blue fluorescence during.

[0010] The amount of visible light produced by the fluorescence of any of the adhesive compositions of the present invention may be a single or a combination of a number of variables, such as the concentration of the fluorescent agent in the adhesive, the amount used in the detection. The thickness of the adhesive layer, the particular substrate used, etc. For example, in thin films having a thickness in the range of 0 to about 100 μm, it should be understood that the amount of visible light that can be emitted from the adhesive of the present invention is typically linear with respect to the thickness of the adhesive. . However, it should be understood that as the adhesive film thickness increases, the correlation between the amount of visible light produced and the absolute film thickness becomes non-linear.

[0011] Fluorescent agents suitable for use in the present invention are Ullman's Encyclopedia.
of Industrial Chemistry) Vol.A18 (5th edition) No. 153
On pages 167, such as distyrylbenzene, distyrylbiphenyl and divinylstilbene,
Triazinylaminostilbene, styylbenzyl-2
H-triols such as stilbenyl-2H-naphtho [1,2-d] triazole and bis (1,2,3-triazol-2-yl) stilbene, benzoxazoles such as stilbenylbenzoxazole and bis (benzoxazole ), Furan and benzo [b] furan, such as bis (benzo [b] furan-2-yl) biphenyl, and benzimidazole, such as cationic benzimidazole, 1,3-diphenyl-2-pyrazoline, coumarin, naphthalimide and 1 And those conventional in the art, including 3,3,5-triazin-2-yl derivatives and mixtures thereof. Another suitable fluorescent agent suitable for use in the compositions of the present invention is Ciba.
European Patent Application EP-A under the name of Specialty Chemicals Holding, Inc.
It is described in detail in the specification of -0682145.

The light emitting material or mixture thereof typically comprises from about 0.001% to about 1%, preferably from about 0.01% to about 0.8% by weight of the light emitting adhesive composition. %, More preferably from about 0.05% to about 0.5%, and especially from about 0.08% to about 0.2% by weight.

Adhesive Material (1) (i) Acrylic Adhesive The acrylic adhesive can be cured by the action of heat and / or light. In this case, the acrylic adhesive is usually formulated as a one-component system. Examples of suitable acrylic adhesives for use in the present invention are those conventional in the prior art.

Acrylic resins suitable for use in the compositions of the present invention include at least two of the following formulas: CH ₂ ＣＲCR ³ —COO— (I) wherein R ³ is a hydrogen or chlorine atom, or methyl Which represents a group or an ethyl group].

Suitable esters having at least two groups of the formula (I) are esters, especially aliphatic, cycloaliphatic, cycloaliphatic, araliphatic or heteroaliphatic polyhydric alcohols, especially diols. And acrylates and methacrylates of triols; polyhydroxy-, especially dihydroxy-carboxylic acids; polyhydroxy-, especially dihydroxy-alkylamines; and polyhydroxy-, especially dihydroxy-alkylnitrile. Acrylic esters-urethanes and -ureides may also be used. Such esters are usually commercially available and none of them need be prepared by known methods.

Suitable acrylic esters have the formula:

Embedded image [Wherein, R ³ has the same meaning as defined in the text, and R ⁵ represents —H, —CH ₃ , —C ₂ H ₅ , —CH
₂ OH, or the following formula:

Embedded image Wherein R ⁴ is —H, —OH, or the following formula:

Embedded image Wherein x represents an integer of 1 to 8, b represents an integer of 1 to 20, and c represents 0 or 1.].

Among the compounds represented by formula (II), compounds wherein x represents an integer of 1 to 4, b represents an integer of 1 to 5, and R ³ represents a hydrogen atom or a methyl group. preferable. Particular examples of such compounds are ethylene glycol, propylene glycol, butane-
1,4-diol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, diacrylate and dimethacrylate of tetrapropylene glycol.

Other suitable acrylic esters have the formula:

Embedded image Wherein b, c, R ³ and R ⁴ have the same meaning as defined above, d represents 0 or a positive integer, provided that c and d do not represent 0, and e represents 2, 3, or 4 and R ⁶ is a carbon atom or a valence e linked through its carbon atom to the indicated b oxygen atoms
Represents an organic group of the formula:

Preferred among the compounds represented by formula (III) are those wherein b, c and d each represent 1,
Compounds in which ³ represents a hydrogen atom or a methyl group and R ⁶ represents a hydrocarbon residue of an aliphatic polyhydric alcohol having 2 to 6 carbon atoms, for example a pentaerythrityl group. A particular example of such a compound is pentaerythrityl tetrakis (dimethylene glycol acrylate).

Still other suitable esters are of the formula:

Embedded image Wherein c and e have the same meanings as defined above, R ⁷ represents —H or —CH ₃ , and R ⁸ is, other than a carbon atom, through that carbon atom of a carbonyl group. And represents an organic group having a valence of e).

More specifically, where c represents 0, R
⁸ may represent a residue of an alcohol or phenol having a hydroxyl group containing 1 to 60 carbon atoms.

R ⁸ is therefore an aromatic, araliphatic, aliphatic-aromatic, cycloaliphatic, heterocyclic or heterocycloaliphatic radical, for example a chlorine atom, a bromine atom or, if desired, 1 to 9 An aromatic group containing only one benzene ring, or an oxygen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, which is substituted by an alkyl group having 1 to 4 carbon atoms Aromatic group consisting of a chain of two to four benzene rings, or a sulfone group in which each benzene ring is optionally substituted by a chlorine atom, a bromine atom or an alkyl group consisting of one to nine carbon atoms Or a saturated or unsaturated, straight-chain or branched-chain aliphatic group, which may further contain an oxygen bond and may be substituted by a hydroxyl group, in particular from 1 to 8 May represent a saturated or monoethylenically unsaturated straight chain aliphatic hydrocarbon radical consisting atom.

Particular examples of such groups are those of the formula -C ₆ H ₄
C (CH ₃ ) ₂ C ₆ H ₄ — [e represents 2], and —C ₆ H ₄ (CH ₂ C ₆ H ₃ ) _f —CH ₂ C
₆ H ₄ - in [wherein, f is 1 or 2, in this case, e
Represents 3 or 4] and a group represented by the formula —CH ₂ CHCH ₂ — or —CH ₂ CH (CH ₂ )
_3- [in this case, e represents 3] or the formula-(CH
_{2) 4 -, - CH 2} CH = CHCH 2 -, - CH 2 CH
₂ OCH ₂ CH ₂ — or — (CH ₂ CH ₂ O) ₂ CH
An aliphatic group represented by ₂ CH ₂ — (e represents 2 in this case).

When c represents 1, R ⁸ is a residue of an acid having a carbonyl group containing 1 to 60 carbon atoms, preferably saturated or 1 to 20 carbon atoms. Ethylenically unsaturated, straight-chain or branched-chain aliphatic hydrocarbon radicals which may be substituted by chlorine atoms and interrupted by oxygen atoms and / or by carbonyloxy (-COO-) groups Or a saturated or ethylenically unsaturated, alicyclic or aliphatic-alicyclic hydrocarbon group of at least 4 carbon atoms, which may be substituted by a chlorine atom; or
It may represent an aromatic hydrocarbon radical of 6 to 12 carbon atoms, which may be substituted by chlorine or bromine atoms.

Another preferred compound in which c represents 1 is that R ⁸ is a saturated or ethylenically unsaturated, straight-chain or branched-chain fatty acid consisting of 1 to 8 carbon atoms. A saturated or ethylenically unsaturated, straight-chain hydrocarbon group, which is optionally substituted by a hydroxyl group, or consisting of 4 to 50 carbon atoms and interrupted by a carbonyloxy group Or branched aliphatic hydrocarbon group, or a saturated or ethylenically unsaturated, monocyclic or bicyclic alicyclic hydrocarbon group having 6 to 8 carbon atoms, or 10 to 51 A compound which represents an ethylenically unsaturated, alicyclic-aliphatic hydrocarbon group having six carbon atoms, or a monocyclic aromatic hydrocarbon group having six to eight carbon atoms. Specific examples of the residue consisting of carboxylic acids of the formula -CH ₂ CH ₂ -,
—CH ＝ CH— and —C ₆ H ₄ — (in this case, e is 2
Represents a group).

Specific examples of suitable compounds of the formula (IV) are epoxy acrylates such as 1,4-bis (2-hydroxy-3 (acryloyloxy) propoxy) butane, bis (4-hydroxyphenyl) Methane poly (2-hydroxy-3 (acryloyloxy) propyl) ether (bisphenol F), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and phenol-formaldehyde novolak, bis (2-hydroxy-3) -Acryloyloxypropyl) adipate and methacryloyloxy compounds of these compounds.

(Ii) Urethanes and other suitable esters are of the formula:

Embedded image Wherein R ³ has the same meaning as defined above, and R ⁹ is a carbon atom or the indicated -O- and -X- X represents a monovalent aliphatic, alicyclic, aromatic, or araliphatic group, and X represents —O—, —NH—, or —N (alkyl) —.
Wherein the alkyl group has 1 to 8 carbon atoms, g represents an integer of at least 2, and at most 6, and R ¹⁰ is a carbon atom or a group of carbon atoms of the indicated NH group. G-valent alicyclic, aromatic, linked via
Or an araliphatic group].

Preferably, R ⁹ represents a divalent aliphatic radical of 2 to 6 carbon atoms, and R ¹⁰ represents one of the following radicals:

A divalent aliphatic group consisting of 2 to 10 carbon atoms, for example:-(CH ₂ ) _6- , -CH ₂ C
_{(CH 3) 2 CH 2 CH} (CH 3) (CH 2) -, or _{-CH 2 CH (CH 3) CH} 2 C (CH 3) 2 (C
H _{2) 2} - group represented by, or optionally, a phenylene group substituted by a methyl group or a chlorine atom; a naphthylene group; the _{formula: -C 6 H 4 C 6 H} 4 -, - C 6 H 4 CH
₂ C ₆ H ₄ — or —C ₆ H ₄ C (CH ₃ ) ₂ C ₆ H ₄
Or a mononuclear alkylcycloalkylene or alkylcycloalkylalkylene group having 6 to 10 carbon atoms, for example, methyl-cyclohex-2,4-ylene, methyl-cyclohexyl-
2,6-ylene group or 1,3,3-trimethylcyclohex-5-ylenemethyl group.

The specific compound represented by the formula (V) is
2,4- and 2,6- (bis (2-acryloyloxyethoxycarbonamide) toluene and the corresponding methacryloyloxy compounds.

(Iii) Peroxyacrylate Another suitable acrylic ester is of the formula:

Embedded image Wherein R ³ has the same meaning as defined above, and R ¹¹ is CH ₃ —, C ₂ H ₅ —, —CH ₂ OH
Or CH ₂ ＣC (R ³ ) COOCH ₂ — and R ¹² represents —CH ₂ OH or —CH ₂ OOC— (R ³ ) =
CH ₂ —, especially 1,1,1-trimethylolpropane triacrylate group, pentaerythritol tetra-
Acrylate group and the corresponding methacrylate group].

Yet another suitable acrylic ester is of the formula:

Embedded image [R ³ represent the same meanings as defined above, R ¹³ represents -H, a -CH ₃ or -CH ₂ Cl,
And R ¹⁴ is each a group —COOCH (R ¹³ ) CH ₂ OO
CC (R ³⁾ = after excluding the four carbonyl groups are directly bonded to a carbon atom CH ₂ and the indicated set of groups -COOH are adjacent, from carbon atoms and one or up to 20 Many carbocyclic

Preferably, R ³ and R ¹³ are -H or -C
H ₃ and R ¹⁴ is one or two benzene rings, especially a pyromellitic acid group or benzophenone-3,
Represents a residue of an aromatic tetravalent carboxylic acid having a 3 ', 4,4'-tetracarboxylic acid group.

(2) Epoxy Adhesives Epoxy adhesives can exist as one or two component adhesive systems. Epoxy adhesives, typical curing agents (aliphatic amines,
Binary systems, including aromatic amines, acid anhydrides and other curing agents) are well known in the art. Epoxy adhesives, one-component adhesives including suitable curing agents (including iodonium, sulfonium and ferrosium salts) include:
It is cured by irradiating ultraviolet rays.

Examples of epoxy adhesives suitable for use in the compositions of the present invention include the following: polyglycidyl esters, polyglycidyl ethers, cycloaliphatic epoxides, and mixtures thereof.

Examples of epoxides which can be used are preferably, on average, more than one of the following formulas directly bonded to oxygen or nitrogen atoms or atoms:

Embedded image [Wherein, R ¹ represents a hydrogen atom or a methyl group].

Examples of such epoxides include compounds containing two or more carboxylic acid groups per molecule and epichlorohydrin, glycerol dichlorohydrin, or β-methyl epichlorohydrin in the presence of an alkali. And poly (β-methylglycidyl) ester obtained by the reaction with The polyglycidyl ester is an aliphatic polycarboxylic acid such as oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
From dimers or trimers of suberic, azelaic, sebacic, or linoleic acid; cycloaliphatic polycarboxylic acids such as tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid, and 4-methyl It can be derived from hexahydrophthalic acid; and from aromatic polycarboxylic acids such as phthalic acid and terephthalic acid.

Another example is the use of compounds containing at least two free alcoholic and / or phenolic hydroxyl groups per molecule under alkaline conditions, or alternatively in the presence of an acidic catalyst, with suitable epichlorohydrins. Polyglycidyl and poly (β-methylglycidyl) ether obtained by reacting and then treating with alkali. Said ethers are acrylic alcohols such as ethylene glycol, diethylene glycol and higher poly (oxyethylene) glycol, propane-1,2-diol and poly (oxypropylene) glycol, propane-1,3-diol, butane-1,
4-diol, poly (oxytetramethylene) glycol, pentane-1,5-diol, hexane-1,6-
From diols, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane, pentaerythritol, sorbitol, and polyepichlorohydrin; alicyclic alcohols such as resorcitol, quinitol, bis (4 -Hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) propane, and 1,1-bis (hydroxymethyl) cyclohex-3-ene; and alcohols having an aromatic nucleus, such as 2,4- ( (Dihydroxymethyl) benzene. They are derived from mononuclear phenols such as resorcinol and hydroquinone, and polynuclear phenols such as bis (4-hydroxyphenol) methane, 4,4'-dihydroxydiphenyl,
1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl)
From propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and from aldehydes, such as formaldehyde, acetaldehyde, chloral, and furfuraldehyde, acetaldehyde and phenols, such as phenol itself, and chlorine atoms or each A phenol whose ring is substituted by an alkyl group containing up to 9 carbon atoms, for example 4-chlorophenol,
It can also be made from novolaks formed from 2-methylphenol and 4-tert-butylphenol.

Epoxides in which some or all of the epoxy groups are not terminal, such as vinylcyclohexane dioxide, limonene dioxide, dicyclopentadiene dioxide, 4-oxatetracyclo [6.2.1.
0 ^2,7 . 0 ^3,5 ] undec-9-ylglycidyl ether or ethylene glycol, 3,4-epoxycyclohexylmethyl 3 ', 4'-epoxycyclohexanecarboxylate and its 6,6'-dimethyl derivative, bis (3,3) 4-epoxycyclohexane-carboxylate), 3- (3,4-epoxycyclohexyl) -8,9-epoxy-2,4-dioxaspire [5,5] undecane, and epoxidized butadiene or butadiene and an ethylenic compound; For example, copolymers of styrene and vinyl acetate may be used.

1,2 bonded to different types of heteroatoms
Epoxy resins having epoxy groups, such as glycidyl ether-glycidyl esters of salicylic acid, may also be used.

Preferred epoxides are 2,2-bis (4-
Hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane or formaldehyde and phenol, or by one chlorine atom, or by 1 to 9
Novolaks derived from phenols substituted by one alkyl hydrocarbon containing one carbon atom,
And polyglycidyl esters of novolak, polyglycidyl ethers having a 1,2-epoxide content of at least 0.5 equivalent per kilogram, and 3,4-epoxycyclohexylmethyl 3 ', 4'-epoxycyclohexanecarboxylate.

Preferably, the adhesive material or mixture thereof comprises at least 90%, more preferably from about 90% to about 99.999%, and especially from about 99.90% to about 99.99% of the light emitting material of the present invention. Contains 98%.

Photocurable Adhesive Compositions Preferred adhesives for use in the compositions of the present invention are photocurable adhesives. In particular, photocurable adhesives comprising an adhesive material in combination with a light emitting substance as well as a photoinitiator are particularly preferred.

A preferred photocurable adhesive composition suitable for use in the present invention is (I) a photocurable material having, on average, more than one acrylic group per molecule, wherein at least one of said materials. About 20% to about 70%,
Photocurable wherein preferably about 30% to about 60%, more preferably about 40% to about 55%, and especially about 45% to about 50% is urethane acrylate, polyester acrylate or a mixture of urethane acrylate and polyester acrylate. Substance, if desired
(II) a solid polyvinyl acetal as the sole or main solid film-forming component; (III) a photoinitiator for photopolymerization of an acrylic compound; and (IV) an adhesive comprising a light emitting substance.

Preferred photocurable adhesives for use in the present invention include aliphatic, cycloaliphatic or aromatic urethane acrylates and mixtures thereof. In general, good results have been obtained with aliphatic and cycloaliphatic urethane acrylates. The urethane acrylate is a reaction product of a polyisocyanate, in particular, a material having on average more than one isocyanate group per molecule with a material having at least one hydroxyl group and at least one polymerizable acrylic group. May be. For example, it may be an adduct of aliphatic and cycloaliphatic diisocyanates and epoxy resins, for example the reaction product of 1,4-butanediol diglycidyl ether with acrylic acid or methacrylic acid. Alternatively, said urethane acrylate is a reaction product of a polyol, especially a material having on average more than one hydroxyl group per molecule, with a material having at least one isocyanate group and at least one polymerizable acrylic group. May be a thing;
For example, it can be polyoxyalkylene glycol and 2-
It may be a reaction product with isocyanatoethyl methacrylate.

A preferred group of photopolymerizable polyurethanes is
It is a reaction product of (A) an isocyanate-terminated polyurethane prepolymer and (B) a hydroxyl group-containing acrylic compound. Isocyanate-terminated polyurethane prepolymers are commercially available or can be obtained by already established methods. They can be prepared, for example, by reacting a polyol, such as a hydroxyl-terminated polyether or polyester, or a polyamine, such as a polyoxyalkylene polyamine, with a stoichiometric excess of a polyisocyanate, such as an aliphatic or cycloaliphatic polyisocyanate. May be manufactured.

Preferred isocyanate-terminated prepolymers (A) are the reaction products of polyoxyalkylene glycols with diisocyanates. Suitable polyalkylene glycols include diols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxypropylene glycol obtained by reacting 1,4-butanediol, neopentyl glycol or 1,6-hexanediol with ethylene oxide or propylene oxide. Tetramethylene glycol, polyoxyalkylene glycol, and mixtures of two or more thereof; polyoxyethylene glycol and polyoxypropylene glycol are preferred, including those having a molecular weight of 1000 or greater.

The diisocyanate to be reacted with the polyalkylene glycol is an aliphatic diisocyanate, such as 1,2-propylene, 1,3-propylene,
1,2-butylene-, 1,4-butylene-, pentamethylene-, hexamethylene-, 2,4,4-trimethylhexamethylene-, 2,2,4-trimethylhexamethylene- and dodecamethylene-diisocyanate; Cyclic diisocyanates such as 1,3-cyclohexylene- and 1,4-cyclohexylene-diisocyanate, methyl-2,4-cyclohexylenediisocyanate, methyl-2,6-cyclohexylenediisocyanate,
3-bis (isocyanatomethyl) cyclohexane, 1,
4-bis (isocyanatomethyl) cyclohexane, 3-
Isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 4,4'-methylenebis (cyclohexyl isocyanate); and aromatic diisocyanates such as m-
And p-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate, 1-chloro-2,
It may be 4-diisocyanatobenzene, 1,4-naphthalenediisocyanate, 4,4'-diphenylmethane diisocyanate and 4,4'-diphenyl ether diisocyanate. Mixtures of two or more of the above diisocyanates may be used. Among the diisocyanates, diphthalic acid and alicyclic diisocyanate are preferable, and isophorone diisocyanate is particularly preferable.

The hydroxyl group-containing acrylic compound which reacts with the isocyanate-terminated prepolymer is preferably a hydroxyalkyl acrylate or a hydroxyalkyl methacrylate such as hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
-Hydroxypropyl acrylate, 4-hydroxybutyl acrylate and the corresponding methacrylates.
Particularly preferred compounds are 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.

The reaction between the isocyanate-terminated prepolymer and the hydroxyl group-containing acrylic compound to obtain a photocurable urethane acrylate can be carried out, for example, in an inert solvent in the presence of a polymerization inhibitor, such as hydroquinone, for 30 to 30 hours. Heating to 110 ° C. may be performed using conventional methods.

[0051] Photocurable urethane acrylates of the above type are commercially available. For example, they are under the trade name Ebecryl (RTM) and under the name IRR,
Available from UCB. They have the trade name Actacryl
Under the name (Actocryl) (RTM) and under the name LPX, also from Ancomer, the trade name Photomer
It is also available from Harcros under the (RTM) and from Craynor under the trade name Sartomer (RTM).

The photocurable polyester acrylates used as part of all photocurable compounds (I) have been modified after being formed by reactions introducing on average more than one acrylic group per molecule. It may be polyester. For example, the polyester acrylate may be a reaction product of a hydroxyl-terminated polyester and an acrylic compound having a hydroxyl-reactive group, which is a carboxyl group, a carboxylic acid halide group or an epoxy group.

The hydroxyl-terminated polyesters which can be acrylated as described in the text include the reaction products of dihydric alcohols with stoichiometric amounts of dicarboxylic acids or anhydrides or halides. Suitable dihydric alcohols for the preparation of the polyesters are alkylene glycols, for example ethylene glycol, 1,2-
Propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, and 1,6-hexanediol; oxyalkylene glycols such as the above-mentioned alkylene glycols or dihydric phenols and ethylene oxide or propylene oxide, diethylene glycol, Triethylene glycol,
Includes reaction products with higher polyoxyethylene glycol, dipropylene glycol, tripropylene glycol, higher polyoxypropylene glycol and polyoxytetramethylene glycol (polytetrahydrofuran). Suitable dicarboxylic acids and anhydrides for producing the polyesters are fatty acids and anhydrides, such as succinic acid, succinic anhydride, glutaric acid, glutaric anhydride, adipic acid, pimelic acid, suberic acid, azelaic acid, Sebacic acid, maleic acid, maleic anhydride and fumaric acid; cycloaliphatic acids and anhydrides, such as tetrahydrofumaric acid, hexahydrofumaric acid and their anhydrides; and aromatic acids and anhydrides, such as phthalic acid, phthalic acid Includes acid anhydrides, isophthalic acid and terephthalic acid.

Other hydroxyl-terminated polyesters which can be acrylated as described in the above text are the reaction products of polyhydric alcohols or alkylene oxides with carboxyl-terminated polyesters, where carboxyl-terminated polyesters are used. Polyesters are the reaction products of dihydric alcohols, such as those described herein, with a stoichiometric excess of dicarboxylic acids or anhydrides, such as those described above, or dicarboxylic acids or anhydrides,
For example, it may be the reaction product of the above and a hydroxyl-terminated polyester derived from a dihydric alcohol and a dicarboxylic acid as described above. Hydroxyl-carboxyl to obtain end-capped polyester
Suitable polyhydric alcohols for reaction with end-capped polyesters are the dihydric alcohols mentioned above and the highly functional polyhydric alcohols, such as trimethylolethane, 1,1,1-trimethylolpropane, pentaerythritol, dipentaerythritol Sorbitol and adducts of said highly functional polyhydric alcohols with ethylene oxide or propylene oxide. Suitable alkylene oxides for reaction with a carboxyl-terminated polyester to obtain a hydroxyl-terminated polyester are ethylene oxide and propylene oxide.

Hydroxyl-reactive acrylic compounds that react with hydroxyl-terminated polyesters to form polyester acrylates include acrylic acid, acryloyl chloride, methacrylic acid, methacryloyl chloride, glycidyl acrylate, glycidyl methacrylate, hydroxyalkyl acrylate or hydroxyalkyl. 1 mol of methacrylate and 1 of dicarboxylic anhydride
It may be a reaction product with a mole or an acid halide of the reaction product. Preferably, said hydroxyl-reactive acrylic compound is acrylic acid, methacrylic acid, acryloyl chloride or methacryloyl chloride.

Other photopolymerizable polyester acrylates that can be used include carboxyl-terminated polyesters,
It is a reaction product with an acrylic compound having a carboxyl-reactive group, which is a hydroxyl group or an epoxy group. Suitable carboxyl-terminated polyesters include those derived from dihydric alcohols and stoichiometric excesses of dicarboxylic acids or anhydrides as described above. Other suitable carboxyl-terminated polyesters are hydroxyl-terminated polyesters, such as those described above, and polycarboxylic acids or halides or anhydrides thereof, such as the dicarboxylic acids and anhydrides described above, and high-functional acids and anhydrides. For example, reaction products of trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their anhydrides. The carboxyl-reactive acrylic compound that is reacted with the carboxyl-terminated polyester to form a photopolymerizable polyester acrylate is a hydroxyalkyl acrylate or hydroxyalkyl methacrylate such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxy It may be propyl acrylate, 4-hydroxybutyl acrylate, and the corresponding methacrylate, glycidyl acrylate or glycidyl methacrylate.

Examples of suitable polyesters as described in the above text are described in US Pat.
No. 206025. Suitable polyester acrylates are trade names Ebecryl
It is commercially available from UCB under (RTM).

The urethane acrylate and / or polyester acrylate may contain substantially all of the photocurable substance (I). If a mixture of urethane acrylate and polyester acrylate is used, the weight ratio of urethane acrylate to polyester acrylate may be from 1:99 to 99: 1. Alternatively, the photocurable substance (I) comprises a mixture of urethane acrylate and / or polyester acrylate and polyacrylic ester of monomeric polyhydric alcohol, polyacrylic ester of polyether polyol or polyacrylic ester of epoxy resin. Is fine. The polyacrylic ester is present in an amount of 0.1 to 80% by weight of the mixture, for example, 5 to 75%, 10 to 75%, 20 to 75%, 30 to 75%, 40 to 7%.
It may consist of 5%, 50-75% or 60-75% by weight.

Examples of polyacrylic esters of monomeric polyhydric alcohols are glycol polyacrylates and polymethacrylates, and alkylene glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4 -Butanediol, neopentyl glycol and 1,6-hexanediol, and oxyalkylene glycols such as diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol; and highly functional alcohols such as glycerol, 1,
1,1-trimethylol, pentaerythritol and polyacrylates and polymethacrylates of adducts of the alcohols with ethylene oxide or propylene oxide. Suitable polyacrylic esters of the polyether polyols include polyacrylates and polymethacrylates of polyols such as polyoxyethylene glycol, polyoxypropylene glycol and polyoxytetramethylene glycol (polytetrahydrofuran). Examples of polyacrylic esters of epoxides are:
Adducts of acrylic acid or methacrylic acid with polyhydric alcohols, such as the polyglycidyl ethers of the abovementioned polyhydric alcohols, or polyhydric phenols, usually bisphenols, such as bisphenol A or polyglycidyl ethers of novolak resins. Polyacrylic esters of monomeric alcohols and polyacrylic esters of epoxide resins are preferably used together with urethane acrylates and / or polyester acrylates, particularly preferably the polyacrylic esters are 1,4-butanediol diacrylate and precursors. A diglycidyl ether of bisphenol A, especially bisphenol A-produced.

Mixtures of photopolymerizable polyurethanes and photopolymerizable polyesters as described in the above text can be used as the adhesive component of the light emitting composition of the present invention.

The photocurable acrylic substance (I) is composed of 100% by weight of acrylic urethane resin, 100% by weight of polyester acrylate, or 95% of polyester acrylate.
From 50 to 50% by weight, especially from 95 to 85% by weight,
Urethane acrylate 5 to 50% by weight, especially 5
Or 20 to 40% by weight, especially 25 to 35% by weight, of urethane acrylate and 80 to 60% by weight, especially 75 to 65% by weight, of polyacrylates of monomeric polyhydric alcohols.
% By weight, or polyester acrylate 5
0 to 70% by weight, especially 55 to 65% by weight
And polyacrylester 50 to 3 of epoxy resin
It may consist of a mixture with 0% by weight, especially 45-35% by weight.

The desired film-forming component, polyacetal (II), can be, for example, polyvinyl formal, polyvinyl acetal or polyvinyl butyral.
Suitable such polymers are commercially available. Polyvinyl butyral, especially at least 150 ° C., for example 15
Those having a softening point in the range of 0 to 180 ° C or at least 200 ° C are preferred. As noted above, the polyvinyl acetal is the sole or major solid film forming component of the film adhesive of the present invention. The amount selected for a particular adhesive is such that the adhesive is a solid, free-standing film. As will be apparent to those skilled in the art, this amount may vary depending on the nature of the photocurable acrylic material (I), the nature of any desired auxiliary components of the film adhesive, and their amounts. The optimal amount of polyvinyl acetal (II) for a particular adhesive can be prepared by simple experience. Usually, the polyvinyl acetal is present in an amount of 20 to 150% by weight of the photocurable acrylic (I).

If desired, the film adhesives of the present invention may be used with other solid film-forming polymers, such as olefin-vinyl ester copolymers, such as ethylene-vinyl acetate copolymers, olefin-alkyl acrylate copolymers, such as ethylene-ethyl acrylate copolymer, other It may include an acrylic polymer, a phenoxy resin, a precursor epoxy resin or a (non-acrylated) polyurethane.

Another photopolymerizable acrylic substance that may be included in the composition of the present invention is an adduct of acrylic acid or methacrylic acid and an epoxy resin, wherein the epoxy resin has an alicyclic ring carbon atom. Cycloaliphatic epoxy resins with attached epoxy groups or, preferably, polyhydric alcohols, such as polyglycidyl ethers of the alcohols described herein or polyhydric phenols, especially bisphenols, such as bisphenol A or bisphenol F
Or polyglycidyl ethers of phenol novolak resins, and precursors of, for example, polyglycidyl ethers, i.e., precursors prepared by reacting, for example, polyglycidyl ether with a difunctional reactant, such as a dihydric alcohol or a dihydric phenol. Epoxy resin.

The photopolymerizable polyurethane and / or polyester (I) generally comprises at least about 20% to about 70%, preferably about 30%, by weight of the light emitting adhesive composition.
% To about 60%, more preferably about 40% to about 55%, and especially about 45% to about 50% by weight. If the liquid composition comprises an acrylic monomer reactive diluent, it is usually
About 5% to about 70% by weight of the light emitting adhesive composition
Preferably from about 20% to about 65%, more preferably from about 30% to about 60%, most preferably from about 50% to about 60% by weight. The photopolymerizable initiator (III) is usually used in a conventional amount, usually about 0.01% to about 20%, preferably about 0.1% to about 20% by weight of the total photopolymerizable acrylic component of the liquid composition. 10% by weight, more preferably about 0.1% to about 5% by weight, and most preferably about 1% to about 5% by weight, ie, with any other photopolymerizable acrylic material, Present in the composition. Suitable amounts of polyvinyl acetal can be readily determined by simple experience; usually, it will be between 0.2 and 20 of the present adhesive composition.
%, Preferably 0.5 to 10% by weight.
Similarly, the amount of any reinforcement to be included in the composition may be selected to achieve the desired degree of reinforcement; typically, the reinforcement is from 0.2 to 20 parts of the liquid composition. %, More preferably 1 to 10% by weight.

Curing of the Adhesive (I) Chemical Curing As described in the text above, some adhesives can be cured using a chemical curing agent. To avoid ambiguity, hardeners and chemical hardeners are used interchangeably herein. Suitable chemical hardeners for use in the adhesive system of the present invention include: hardeners derived from polyamines having 2 to 10 amino groups, preferably 3 to 6 amino groups; Standard and well-known chemical curing agents in the prior art are included, including curing agents derived from polythiols having 2 to 6 amino groups, preferably 2 to 4 amino groups.

Another chemical curing agent suitable for use in the present invention includes ketone block polyamide.
Ketone block polyamides (sometimes called ketimines) are made by condensing an amine with a ketone to make an alkyl nitrilo (1-alkyl) alkylidine compound.

For example, two moles of a ketone are reacted with diethylenetriamine to give

Embedded image Two primary amines give the protected compound. In this case, the reaction of the imine with one mole of phenylglycidyl ether removes the active hydrogen atom of the secondary amine, as there are still reactive hydrogen atoms.

Embedded image

The compounds are very non-reactive when incorporated into the composition. However, due to the instability of the double bond in the compound against hydrolysis, once the composition is used, hydrolysis occurs due to moisture in the air and the regenerated primary amine is cured. Cause. The regenerated ketone diffuses to the surface and then volatilizes.

The regenerated amine is composed of the acrylic resin and
Reacts very quickly, even at room temperature. This causes rapid solidification of the adhesive, thereby holding the bonding adhesive in place while the epoxy is cured by the amine.

The curing agent may be derived from a polyamine having 2 to 10 amino groups, preferably 3 to 6 amino groups. The ketone protecting group has the formula R ₁ R ₂ CO =
O (wherein R ₁ and R ₂ are independently 1 to 10
, Preferably representing an alkyl group having 2 to 6 carbon atoms).

(Ii) The adhesive composition which can be cured by the action of heat curing heat preferably comprises at least one free radical polymerization initiator. The free radical polymerization initiator may be any of the known free radical-generating initiators commonly used in vinyl polymerization, and is preferably an organic peroxide or azo compound. The initiator is used in a conventional amount, usually 0.01 to 1 of the polymerizable substance.
5% by weight, preferably 0.05 to 10% by weight, more preferably about 0.1 to about 5% by weight and especially about 0.5 to about 4% by weight may be used. Suitable organic peroxides are dialkyl peroxides such as tert-butyl peroxide and 2,2-bis (tert-butylperoxy) propane, diacyl peroxides such as benzoyl peroxide and acetyl peroxide, peresters such as Tributyl perbenzoate and tert-butyl per-2-ethylhexanoate, purge carbonates such as dicetylperoxydicarbonate and dicyclohexylperoxydicarbonate, ketone peroxides such as cyclohexanone peroxide and methyl ethyl ketone peroxide, and hydroperoxide For example, cumene hydroperoxide and tertiary butyl hydroperoxide. Suitable azo compounds are azobis (isobutyronitrile) and azobis (2,4-
Dimethylvaleronitrile). Accelerators for free-radical polymerization, such as tertiary amines, ketoimines, transition metals, such as cobalt naphthenate, vanadium monobutyl phosphite and sulfimides, may be used with the initiators.

The temperature and time required to heat cure the present adhesive composition will depend on the active ingredient,
And it may be in the range of 80 ° C to 200 ° C.

(Iii) Photocuring As described in detail in the above text, the adhesive composition of the present invention comprises:
It can be cured by light in the presence of a photoinitiator (iii). Photoinitiators or photosensitizers suitable for inclusion herein include: aromatic carbonyl compounds, such as benzoin, benzoin alkyl ethers, such as isopropyl ether or n-butyl ether; a-substituted acetophenones, such as benzyl Ketals, such as benzyldimethyl ketal; a-haloacetophenones, such as trichloromethyl p-tert-butylphenylketone;
Aminoacetophenones such as dimethylaminomethylphenylketone, morpholinomethylphenylketone and E
PA-0003002, EP-A-0088050,
Others as described in EP 0117233 and EP-A-0138754; dialkoxyacetophenones such as diethoxyacetophenone, α, α-dichloroaceto p-phenoxyphenone or a-hydroxy-acetophenone such as 1-hydroxycyclohexyl Phenyl ketone, 1-hydroxycyclohexyl acetophenone, α, α-dimethyl-α-hydroxyacetophenone, p-isopropylphenyl-2-hydroxy-2-methylpropan-1-one, or benzophenone such as benzophenone itself, chlorobenzophenone, 4- Phenylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4,4'-dimethylamino-benzophenone, p-methoxybenzophenone and bis (4-dimethyla Amino) benzophenone; acrylated benzophenone; 4-benzoyl-4'-methyldiphenyl sulfide; aminobenzoates such as amyl p-dimethylaminobenzoate, 2 (n-butoxy) ethyl 4-dimethylaminobenzoate, 2-ethylhexyl-p-dimethyl Aminobenzoates; oximes such as 1-phenyl-1,2-propanedione-2
(O-ethoxycarbonyl) oxime; oxides such as acylphosphine oxides; 9,10-phenanthrenequinone; metallocenes such as titanium metallocenes such as bis (p-methylcyclopentadienyl) bis (s-
Pentafluorophenyl) titanium (IV); an organometallic compound of group IVA together with a photoreducing dye, typically methylene blue or rose bengal, such as stannane,
For example, trimethylbenzylstannane, tributylbenzylstannane or dibutyldibenzylstannane; aliphatic α
Amines having a hydrogen atom bonded to a carbon atom, preferably tertiary amines, such as quinones such as bis (4-dimethylamino) benzophenone and triethanolamine, such as anthraquinone or camphorquinone; thioxanthones such as alkyl- or halogen Substituted thioxanthones, for example 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-dichlorothioxanthone,
2,4-diethylthioxanthone; acylphosphine oxide; or a mixture of two or more thereof.

Preferably, the photoinitiator (III) is an a-substituted acetophenone, thioxanthone, benzophenone or a mixture of two or more thereof. In a particularly preferred embodiment, the initiator is α-hydroxy-substituted acetophenone, α-amino-substituted acetophenone or a mixture thereof with 2-alkylthioxanthone. The photoinitiator is used in conventional amounts, usually from about 0.01% to about 20% by weight of the total photopolymerizable content of the adhesive.
%, Preferably from about 0.1% to about 10%, more preferably from about 0.15% to about 5%, and especially from about 1% to about 5% by weight.

Highly preferred for use in the present invention as a photoinitiator are those of the following formula:

Embedded image [Wherein, m = 1, n = 1 and x = O atom or m = 2, n
= 0 and x = O atom or S atom].

R1 is a linear or branched carbon atom having 1 carbon atom
To 6 alkyl groups, cyclohexyl groups, cyclopentyl groups, phenyl groups, naphthyl groups or biphenyl groups, or one or more F atoms, Cl atoms, Br
Straight chain substituted by an atom, an I atom, an alkyl group having 1 to 4 carbon atoms and / or an alkoxy group having 1 to 4 carbon atoms, a 5- or 6-membered heterocyclic group containing an S atom or an N atom. Or a branched alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, a cyclopentyl group, a phenyl group, a naphthyl group or a biphenyl group.

R2 and R3 which may be the same or different
Is a cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenyl group; one or more F, Cl, Br, I, C1-4 alkyl and / or carbon atoms 5- or 6 containing an alkoxy group of the formulas 1-4, an S atom or an N atom
Represents a cyclohexyl group, a cyclopentyl group, a phenyl group, a naphthyl group or a biphenyl group substituted by a membered heterocyclic group, or R2 and R3 are combined together to form a ring, wherein the Containing 10 carbon atoms and 1 to 6 carbon atoms 1-4
May be substituted with an alkyl group.

A particularly preferred photoinitiator mixture suitable for use in the adhesive composition of the present invention is Ciba Specia under the trade name IRGACURE (RTM) 1800 (Ciba Specia Chemicals).
Irgacure (R) commercially available from
TM) 403 [IRGACURE (RTM) 403] and Irgacure (R
TM) 184 [IRGACURE (RTM) 184].

Another photoinitiator suitable for use in the present invention is ditertiary butyl peroxide, dicumyl peroxide, tertiary butyl hydroperoxide, tertiary butyl peracetate, peracetic acid, perbenzoic acid, Benzoyl peroxide, dichlorobenzoyl peroxide, azobis (isobutyronitrile), dimethylazobis (isobutyrate), morpholine, diethylamine, piperidine,
Pyrrolidine, and the like, and thioxanones such as 2-chlorothioxanone and isopropylthioxanone, tri-isopropylamine, triethylamine,
Includes acylphosphine oxides, bisacylphosphine oxides, 9,10-phenanthrenequinone and 1-phenyl-1,2-propanedione-2 (o-ethoxycarbonyl) oxime.

The actinic radiation used to effect curing of the photocurable adhesive composition of the present invention may preferably be ultraviolet light, or it may emit light in both the visible and ultraviolet regions of the spectrum. Radiation. 2
00 to 800 nm, preferably 200 to 500
Radiation having a wavelength of nm is preferred for use in the present invention. The choice of a suitable radiation source emitting radiation in the said wavelength range from commercial equipment does not pose any problem for a person skilled in the field of photocuring. Suitable sources are
Includes medium pressure mercury arc lamps and metal halide lamps. Suitable irradiation times can be easily and easily determined by those skilled in the art of light curing.

Reactive Diluent The adhesive of the present invention may contain at least one liquid photopolymerizable monovinyl monomer as a reactive diluent. Such diluents can help reduce the viscosity of the composition from which the adhesives of the present invention are made, can be advantageous for subsequent application to a substrate, and then during photocuring of the adhesives To polymerize into Liquid photopolymerizable acrylic monomers are commercially available or can be manufactured by well-known methods.
Suitable liquid photopolymerizable monovinyl monomers include: vinyl esters, eg, vinyl acetate; monoacrylic esters, eg, monoacrylic monomers, including alkyl acrylates and alkyl methacrylates;
For example n-butyl acrylate, 2-ethylhexyl acrylate, n-octadecyl acrylate and the corresponding methacrylates, hydroxyalkyl acrylates and hydroxyalkyl methacrylates, for example 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4
-Hydroxybutyl acrylate and the corresponding methacrylate, acrylic or methacrylic acid and cycloaliphatic monohydric alcohols, especially polycyclic alcohols, such as isobornyl acrylate, dicyclopentenyl acrylate and the corresponding methacrylate; acrylic acid or methacrylic acid , Dihydric alcohols such as ethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, triethylene glycol Esters with polyhydric alcohols including propylene glycol and dimethylolcyclohexane; trihydric alcohols such as glycerol, 1,1,1-trimethylolpropane and trihydroxyethyl isocyanurate; and four or more hydroxyl groups. Polyhydric alcohols, such as erythritol or pentaerythritol, N-vinyl monomers such as N, N-dimethylacrylamide, which are usually, but not exclusively, N-vinyl heterocycles, such as - vinylpyrrolidone or N- vinylcaprolactam; and these two or more mixture. Preferred monovinyl monomers are monoacrylic esters such as those described above, N-vinyl monomers such as those described above and mixtures thereof. Particularly preferred monovinyl monomers are isobornyl acrylate, N-
Vinylpyrrolidone and N, N-dimethylacrylamide. Mixtures of two or more of the above mentioned acrylic components can be used.

The reactive diluent comprises about 5 to about 5 parts of the light emitting composition.
% By weight up to about 70%, preferably from about 20% to about 65%, more preferably from about 30% to about 60%, most preferably from about 50% to about 60% by weight. It may be present in the composition of the invention.

Desired Substances As described in detail in the above text, the adhesive composition of the present invention comprises:
If necessary, it may further contain a desired substance. The desired substances selected for use in the compositions of the present invention may each comprise from about 0.001% by weight to about 10% by weight of the composition of up to about 10% by weight of the composition. About 10
%, Preferably from about 0.01% to about 5%, more preferably from about 0.1% to about 1% by weight in the compositions of the present invention.

An elastomeric polymer may be included as a reinforcement in the film adhesive of the present invention. Reinforced elastomeric polymers are well known in the adhesive art; these include polymers of conjugated dienes such as butadiene or isoprene, which are homopolymers or other ethylenically unsaturated materials, usually styrene, substituted styrene and acrylic. Copolymers with monomers such as acrylonitrile, alkyl acrylates and alkyl methacrylates. These diene polymers may have end-capping functional groups, such as carbonyl groups or vinyl groups. Preferred elastomeric polymers are vinyl-terminated butadiene-acrylonitrile copolymers, especially those having a number average molecular weight of up to 500.

The strength of the film adhesive of the present invention can be adjusted, if desired, in the liquid composition from which the film adhesive is produced.
It can be improved by including a polymer having an aromatic ether group repeatedly in the bone nucleus as a reinforcing material. Such polymers are commercially available or may be prepared by known methods; they are precursor, ie chain extended, for example, a bisphenol having an epoxy equivalent of preferably at least 200, for example the diglycidyl of bisphenol A It includes ethers, phenoxy resins, polyphenylene oxides, aromatic polyether imide resins, and aromatic polyether polyether ketone resins (PEEK resins). Preferred reinforcements have at least 20
Bisphenol A-precursor diglycidyl ethers of bisphenol A having an epoxy equivalent of 0, especially 230 to 300, and phenoxy resins derived from bisphenol A and epichlorohydrin having a molecular weight of 80,000 to 120,000.

If desired, small amounts of conventional additives which do not interfere with the photopolymerization of the composition upon exposure to actinic radiation may be included in the aforementioned liquid compositions. For example, the composition may be a thermal polymerization inhibitor such as hydroquinone or 2,6-di-tert-butyl-4-methylphenol, a dye for evaluating film quality, an adhesion promoter such as silane and a filler such as Powdered glass, which is transparent to actinic radiation
May be included.

Substrate Material First, the adhesive composition of the present invention may be applied to any suitable substrate material. In a preferred use of the composition according to the invention, the composition is applied to a substrate (A) and then to another substrate (B), so that the adhesive composition has between A and B To form a bonding layer. To prevent errors, A and B may be the same material, but may be different materials. Suitable substrate materials for using the compositions of the present invention include those standard and well known in the art.

As discussed earlier in the text, the substrate material can affect the degree of fluorescence observed, or can even prevent the combination of a particular substrate material with a given fluorescent agent. . In the use of the adhesive composition of the present invention, it is preferable that the substrate does not itself contain a fluorescent agent. It is also preferred that the substrate does not have sufficient absorption in both the ultraviolet and visible regions of the spectrum. Therefore,
It is highly preferred in the adhesive composition of the present invention that the fluorescent agent be selected to optimize the transmission region in both the ultraviolet and visible regions of the substrate.

[0090] Preferred substrates for use in the present invention include metallized materials and optionally transparent materials and mixtures thereof.

Typically, the metallization layer is used as a reflection data carrying layer. The thickness of the layer is usually between about 20 nm and about 50 nm, preferably between about 30 nm and about 40 n.
m. Metallized materials suitable for use in the present invention include: aluminum (A
l), silver (Ag), gold (Au) and mixtures thereof; silicon and silicon-based materials such as silicon carbide, silicon nitride and derivatives thereof.

The desired transparent substrate material means any substrate material capable of transmitting at least 5% of light from about 200 nm to about 700 nm in a 10 mm region as defined herein. Examples of desired transparent substrate materials suitable for use in the present invention include:

1. Polymers of monoolefins and diolefins, such as polypropylene, polyisobutylene,
Polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, such as cyclopentene or norbornene, polyethylene (optionally crosslinked), such as high density polyethylene ( HDP
E), high density and high molecular weight polyethylene (HDPE-H)
MW), high density and ultra high molecular weight polyethylene (HDPE)
-UHMW), medium density polyethylene (MDPE), medium density polyethylene (MDPR), low density polyethylene (L
DPE), linear low density polyethylene (LLDPE),
Branched low density polyethylene (BLDPE).

The polyolefins, ie polymers of the monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different methods and in particular by the following methods. a) Radical polymerization (usually performed under high pressure and elevated temperature). b) Catalytic polymerization, usually using a catalyst containing one or more metals of group IVb, Vb, VIb or VIII of the periodic table. The metal usually has one or more ligands, typically oxides, halides, alcoholates, esters, which may be π- or σ-coordinated.
Ether, amine, alkyl, alkenyl and / or aryl. The metal complex may be in free form or may be supported on a substrate, typically on activated magnesium chloride, titanium trichloride, alumina or silicon oxide. The catalyst may be used alone during the polymerization, or another activator, typically a metal alkyl, metal hydride, metal alkyl hydride, metal alkyl oxide or metal alkyl oxane may be used ( Said metal may be a group Ia, IIa and / or
IIIa). The activator may be conveniently modified with another ester, ether, amine or silyl ether. The catalyst system is typically a Phillips catalyst, a Standard Oil Indiana catalyst, a Ziegler (-Natta) catalyst, a TNZ [DuPont
Pont)] catalyst, metallocene catalyst or single site (sin
gle site) It is called catalyst (SSC).

2. 1. A mixture of the polymers described in
For example, a mixture of polypropylene and polyisobutylene,
A mixture of polypropylene and polyethylene (eg, PP
/ HDPE, PP / LDPE) and mixtures of different types of polyethylene (eg LDPE / HDPE).

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene / butene 1-ene copolymer, propylene / isobutylene copolymer, ethylene / but-1-ene copolymer, ethylene / hexene copolymer, ethylene / methylpentene copolymer,
Ethylene / heptene copolymers, ethylene / octene copolymers, propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers and copolymers thereof with carbon monoxide or ethylene / 1. Acrylic acid copolymers and their salts (ionomers), and terpolymers of ethylene with propylene and dienes such as hexadiene, dicyclotentadiene or ethylidene-norbornene; and mixtures of said copolymers with one another and with said copolymers as in 1. Mixtures with the polymers described in e.g. polypropylene / ethylene-
Propylene copolymer (EAA), LLDPE / EV
A, LLDPE / EAA, and alternating or random polyalkylene / carbon monoxide copolymers and mixtures thereof with other polymers such as polyamides.

4. Hydrocarbon resin (for example, having 5 carbon atoms)
To 9) and hydrogenated modifications thereof (eg, tackifiers)
And mixtures of polyalkylenes and starch.

5. Polystyrene, poly (p-methylstyrene), poly (α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with a diene or acrylic derivative, such as styrene / butadiene copolymer, styrene / acrylonitrile copolymer, styrene / alkyl methacrylate copolymer, styrene / butadiene / alkyl acrylate copolymer, styrene / butadiene / alkyl methacrylate copolymer, styrene / Maleic anhydride copolymers, styrene / acrylonitrile / methyl acrylate copolymers; high impact strength mixtures made from styrene copolymers and other polymers such as polyacrylates, diene polymers or ethylene / propylene / diene terpolymers; and block copolymers of styrene For example, styrene / butadiene / styrene block copolymer, styrene / isoprene / Styrene block copolymers, styrene / ethylene / butylene / styrene block copolymer or styrene / ethylene / propylene / styrene block copolymer.

7. Graft copolymer of styrene or α-methylstyrene, for example, graft copolymer of styrene on polybutadiene, graft copolymer of styrene on polybutadiene-styrene copolymer or polybutadiene-acrylonitrile copolymer; graft copolymer of styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; Graft copolymer of styrene, acrylonitrile and methyl methacrylate; graft copolymer of styrene and maleic anhydride on polybutadiene; graft copolymer of styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; graft copolymer of styrene and maleimide on polybutadiene; polybuta Graft copolymer of styrene and alkyl acrylate or methacrylate on ene; graft copolymer of styrene and acrylonitrile on ethylene / propylene / diene terpolymer; graft copolymer of styrene and acrylonitrile on polyalkyl acrylate or polyalkyl methacrylate; styrene and acrylonitrile on acrylate / butadiene copolymer And their graft copolymers. Mixtures with the copolymers described in e.g. ABS polymers,
A copolymer mixture known as MBS polymer, ASA polymer or AES polymer.

8. Halogen-containing polymers such as polychloroprene, chlorinated rubber, chlorinated and brominated copolymers of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and ethylene chloride, epichlorohydrin mono- and copolymers, especially halogen-containing Polymers from vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, and copolymers thereof, such as vinyl chloride / vinyl chloride copolymer, vinyl chloride / vinyl acetate copolymer or vinylidene chloride / acetic acid Vinyl copolymer.

9. Polymers derived from α, β-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, which have been modified with butyl acrylate for improved impact resistance.

10. 9. Copolymers of the monomers mentioned in each other or with other unsaturated monomers, such as acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylates or acrylonitrile / vinyl halide copolymers or acrylonitrile / alkyl methacrylate / butadiene polymer.

11. Polymers derived from unsaturated alcohols and amines or acyl derivatives thereof or acetal thereof, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; 1. And their copolymers with the olefins described in 1.

12. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or their copolymers with bisglycidyl ether.

13. Polyacetals, such as polyoxymethylene and the abovementioned polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with polystyrene and polyamide.

15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as their precursors.

16. From diamines and dicarboxylic acids,
And / or polyamides and copolyamides derived from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10,
6/9, 6/12, 4/6, 12/12, Polyamide 1
1, polyamide 12, aromatic polyamide obtained by condensation of m-xylenediamine and adipic acid; polyamide produced using hexamethylenediamine and isophthalic acid and / or terephthalic acid and optionally an elastomer as a modifier, For example, poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-
Phenylene isophthalamide; and also copolymers of the polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or copolymers with polyethers such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol. And polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (R
IM-polyamide system).

17. Polyureas, polyimides, polyamide-imides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.

18. From dicarboxylic acids and diols,
And / or polyesters derived from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthal, polybutylene terephthal, poly-1,4-
Block copolyetheresters derived from dimethylolcyclohexane terephthalate and polyhydroxybenzoate, and polyethers end-capped by hydroxyl groups; and also polycarbonate or M
Polyester modified with BS.

19. Polycarbonate and polyester carbonate.

20. Polysulfone, polyethersulfone and polyetherketone.

21. Crosslinked polymers derived from aldehydes as one component and phenols, ureas and melamines as other components, such as phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins.

22. Dry and non-dry alkyd resins.

23. An unsaturated polyester resin derived from a saturated or unsaturated dicarboxylic acid, a polyhydric alcohol and a vinyl compound as a cross-linking agent, and a halogen-containing modified product thereof having further low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resin, polyester resin or acrylate resin cross-linked with melamine resin, urea resin, polyisocyanate or epoxy resin.

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, such as the products of glycidyl ethers of bisphenol A and bisphenol F, which are conventional hardeners such as acid anhydrides or Crosslinked with amines and, if desired, with accelerators).

27. Natural polymers, such as cellulose, rubber, gelatin and their chemically modified derivatives, such as cellulose acetate, cellulose propionate and cellulose butyrate, or cellulose ethers, such as methylcellulose; and rosin and derivatives thereof.

28. Compounds of the above-mentioned polymers (polyblends), for example PP / EPDM, polyamide / EPD
M or ABS, PVC / EVA, PVC / ABS, PV
C / MBS, PC / ABS, PBTP / ABS, PC /
ASA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic P
UR, POM / acrylate, POM / MBS, PPO
/ HIPS, PPO / PA6.6 and copolymer, PA
/ HDPE, PA / PP, PA / PPO, PBT / PC
/ ABS or PBT / PEP / PC.

29. Glasses made from silicon dioxide, optionally modified by the inclusion of Na, Ca, B or Pb, in order to obtain properties for a particular use and application.

Some of the above materials were further coated with a thin reflective layer to maintain optical clarity.

Method of Applying Adhesive Composition to Substrate The adhesive composition of the present invention is preferably applied to a substrate material in a thickness of about 0.01 μm to about 200 μm. The method of applying the adhesive, as a layer, to the selected substrate material includes the following: applying the adhesive between two substrates and applying the adhesive between the two substrates. A capillary action in which the flow is controlled by its viscosity; a spin coating in which the adhesive is applied to a flat material and rotated at high speed before or simultaneously with the use of the second substrate to provide a smooth coating; Screen printing wherein the adhesive is applied through a thin mesh to provide a smooth application prior to use of the second substrate; the adhesive is applied to provide a smooth application prior to use of the second substrate Roller coating applied from a roller; K-bar coating wherein the adhesive is applied and spread by using a wire wrapped rod to provide a smooth coating prior to use of the second substrate ;
And a spray application wherein the adhesive is applied in the form of an air-generated aerosol to provide a smooth application prior to use of the second substrate.

As described in the text above, the light emitting adhesive compositions of the present invention are particularly preferred for use in applications where accurate measurement of the binding system is important. One such application is a dual-layer digital universal disc (D
VD).

The term DVD disc, as defined herein, consists of a plurality of layers, at least one of which is a data carrying layer, at least one of which is a tie layer, and at least one of which is a tie layer. One is a protective or covering layer. To avoid errors, the protection or cover layer as defined in the text may contain data information.

The use of the light-emitting adhesive composition as a binding substance in the manufacture of DVDs makes it possible, in practice, to use suitable optical measuring devices to provide a DV for defects in the binding layer.
It has now been found that effective 'in-line' scanning of the D disk is now possible.

In the production of a plastic disc DVD, at least one of which may be covered with a metal layer is bonded together with an adhesive. It is very important in DVD manufacturing that the adhesive bonding the discs together sufficiently covers the data carrying area of the discs. The size and shape of the disc and the area to be covered by the adhesive may vary. Typically, DVD
Is used to avoid continuous production of defective disks.
Manufactured in an environment where line 'process control is desired. However, in practice, visual inspection of the disk with the naked eye to detect defects in the adhesive bond layer of the disk, such as captured air bubbles, is inefficient. It is not possible to detect the degree of control of the 'in-line' joint line thickness with the naked eye. As detailed earlier in the text, accurate 'in-line' coupling line control is very important in DVD manufacturing. The intended coupling line thickness for DVD use is about 20-60 μm, preferably about 50-60 μm, more preferably about 51-59 μm, and especially about 55 μm.

Thus, the light emitting adhesive composition of the present invention provides improved efficiency and improved manufacturing in a multilayer disc manufacturing process. Indeed, it is another aspect of the present invention that scanning of multiple light emitting adhesive layers can be performed through the selection and use of different adhesives of the present invention that include different light emitting layers. Similarly, when a composite multilayer disc is manufactured and provided, it includes layers that are not light-tolerant or substantially non-light-tolerant, and therefore, as described herein. The advantage of bond line control can be used to measure the adhesive on either side of the substantially light unacceptable layer. A layer that is substantially impermissible to light, as described herein, means a layer through which light is not transmitted to an extent that prevents data reading.

In a preferred embodiment of the present invention, the light emitting adhesive is used to bond together two data-bearing disks, which may be made of polycarbonate or the like, wherein One or both of the polycarbonate layers may be coated with a metallized layer on the side to be joined by an adhesive.

In a very preferred embodiment, each polycarbonate layer is metallized. Especially preferred are disks with different metallizations on the polycarbonate layer. This makes it possible to selectively retrieve data from each layer by using an appropriate device.

As described in detail in the text above, the presence of the light emitting adhesive composition of the present invention can be detected by luminescence using a suitable radiation source such as an ultraviolet lamp. Similarly, a radiometer (or other such meter) can be used to measure the visible light emitted from any such system. The presence or absence of bubbles can be detected via simple visual scanning of these emission profiles, or observational enhancement using a computerized scanning system or the like.

One method of determining the bond line thickness of the adhesive is to use any of the disks, preferably including the inner diameter of the bonded disk and the outer diameter of the disk and any desired points in between. Or at a plurality of fixed points.

Another method is to create a representative example of the illuminated disk image and then compare this to a reference example to calculate the deviation correlation. The level of such correlation is greater than about 90%, from 90% to about 95%.
%, Greater than about 95%, such as 95% to about 99%, and may be selected between the manufactured and scanned disc and the reference example according to specific process requirements. A further advantage of such an observation system is the improved response-recognition time in the process line when it is running.

To read the data contained on the two data carrying layers, a laser is usually used. Since the laser is required to read data from at least one metallization layer by reading through the light emitting adhesive layer, to minimize any potential distortion of data reading, The refractive index (RI) is compared to the refractive index of a selected substrate material (eg, a polycarbonate layer).

Preferred adhesive materials for use in making DVD discs are photocurable adhesives, such as acrylic and cationic epoxy adhesives. These are particularly preferred for fast and effective curing. It is further preferred that the adhesive used in disc production has a low shrinkage rate (in curing or during the entire production process).
Usually, shrinkage of less than about 15%, preferably less than about 10%, and more preferably less than about 8% is preferred. In addition, depending on the conditions under which such disks and the like are manufactured, it is preferred that the selected bonding adhesive has environmental resistance. The preferred light emitting adhesive compositions of the present invention are prepared under standard loaded storage conditions (96
Time and 80 ° C. and 95% relative humidity).

[0137]

EXAMPLES AND EFFECTS OF THE INVENTION The following non-limiting examples are:
It is representative of the adhesive composition of the present invention. All of%
Is by weight.

Example 1 In this example, the light emitting adhesive composition of the present invention (adhesive A) was used.
A description will be given of the measurement of the thickness of the glass sheet without defects, as well as the measurement of the light transmitted through the adhesive A when the composition is used to bond two glass sheets together.

Adhesive A Photomer (RTM) 6162 30.0 g Tripropylene glycol diacrylate 12.0 g Phenoxyethyl acrylate 6.5 g Irgacure (RTM) 651 1.5 g Uvitex (RTM) OB 0.036g

Adhesive A was made by mixing the above materials together at room temperature and then leaving them in an oven at about 60 ° C. until a clear solution was obtained.

Adhesive A was cured between a release spray and a glass sheet coated with a suitable spacer, which was then applied to a Fusion lamp (D bulb, 12 spheres).
(0 W / cm) to obtain a thin film after three passes. The thickness of the film was measured with an Elcometer Thickness Gauge (Elc
(Measurement Thickness Gauge).

The samples were placed between two substrates as shown below, then placed on a UVP model UVL-21 "Blak-Ray" UV lamp, and then
Light transmitted through the film at 436 nm and mW / cm ² was measured on a VP Multi-Sense 100 radiometer.

I. 3 mm glass substrate sample thickness (micrometer) Visible light (mW / cm ² ) a 0 0.02 b 20 0.07 c 36 0.10 d 61 0.10

II. 0.6 mm polycarbonate sample thickness (micrometer) Visible light (mW / cm ² ) e 0 0.04 f 20 0.11 g 36 0.15 h 61 0.15

Example 2 In this example, a substantially light-impermeable layer (1.2 mm thick A
l) and the defect-free measurement of the light emitted from the light-emitting adhesive composition (adhesive B) of the invention when placed between a transparent layer (polycarbonate) if desired.

Adhesive B Photomer (RTM) 6162 30.0 g Tripropylene glycol diacrylate 12.0 g Phenoxyethyl acrylate 6.5 g Irgacure (RTM) 651 1.5 g Uvitex (RTM) OB 0.0065g

Adhesive B was prepared by the method described for Adhesive A as detailed in the text above, and then cured between a peel spray and a glass sheet coated with a suitable spacer, After three passes under a Fusion lamp (D bulb, 120 W / cm), a thin film is obtained. The thickness of the film was calibrated on aluminum with an Elcometer Thicness Gauge
Was measured using

[0148] These samples were made of aluminum and 0.6 mm
Place between polycarbonate and then Stove (Sta
ub) Placed under 5000 W electrostatic UV lamp. The light from the stove lamp was filtered using a BLAK-RAY filter, and then a radiometer was placed to measure 436 nm visible light transmitted through the adhesive film.

Sample thickness (micrometer) Visible light (mW / cm ² ) i 0 0.02 j 41 0.05 k 52 0.06 l 104 0.05 where 1) Photomer (RTM) 6162 = Aromatic bifunctional urethane provided by Harcros. 2) Irgacure (RTM) 651 = Photoinitiator provided by Ciba Specialty Chemicals. 3) Uvitex (RTM) OB = Fluorescent substance provided by Ciba Specialty Chemicals

Claims (15)

[Claims] 1. An adhesive composition comprising one or more adhesive components in combination with at least one light emitting substance. 2. The adhesive component comprises the following groups: acrylic adhesive, cyanoacrylic adhesive, epoxy adhesive, polyurethane adhesive, silicone adhesive, cationic adhesive,
An adhesive composition selected from hot melt adhesives, anaerobic adhesives and mixtures thereof. 3. The composition of claim 1, wherein the adhesive component is at least 90%, more preferably from about 90% to about 99.999%, and especially about 99.90% by weight of the adhesive composition.
The composition of claim 1, wherein the composition is from about 99% to about 99.98% by weight. 4. The composition of claim 1, wherein said light emitting material is selected from fluorescent materials, luminescent materials and phosphorescent materials, and mixtures thereof. 5. The method according to claim 1, wherein the light emitting substance is distyrylbenzene,
Distyrylbiphenyl and divinylstilbene, triazinylaminostilbene, styylbenzyl-2H-triol such as stilbenyl-2H-naphtho [1,
2-d] triazole and bis (1,2,3-triazol-2-yl) stilbene, benzoxazole, such as stilbenylbenzoxazole and bis (benzoxazole), furan and benzo [b] furan, such as bis (benzo) [B] furan-2-yl) biphenyl,
And benzimidazoles such as cationic benzimidazole, 1,3-diphenyl 2-pyrazoline, coumarin, naphthalimide and 1,3,5-triazine-
2. The composition according to claim 1, which is a fluorescent substance selected from 2-yl derivatives and mixtures thereof. 6. The method of claim 6, wherein the light emitting material comprises from about 0.001% to about 1% by weight of the adhesive composition, preferably about 0.1% by weight.
Claims: 1 to about 0.8% by weight, more preferably from about 0.05% to about 0.5%, and especially from about 0.08% to about 0.2% by weight. The composition of claim 1. 7. The composition according to claim 1, wherein the adhesive component comprises at least one photocurable adhesive, preferably at least one photocurable adhesive in combination with a photoinitiator. 8. A photocurable material having, on average, more than one acrylic group per molecule, wherein said material is at least about 20% to about 70%, preferably about 3%, of said material.
A photocurable material wherein 0% to about 60%, more preferably about 40% to about 55%, and especially about 45% to about 50% is urethane acrylate, polyester acrylate or a mixture of urethane acrylate and polyester acrylate; The composition according to claim 1, comprising: (II) a solid polyvinyl acetal as the sole or main solid film-forming component; (III) a photoinitiator for photopolymerization of an acrylic compound; and (IV) a light emitting substance. . 9. The photopolymerizable polyurethane and / or polyester (I) is usually at least about 20% to about 70%, preferably about 30% to about 60%, more preferably about 30% by weight of the adhesive composition. 2. The composition of claim 1, wherein is present in an amount of about 40% to about 55%, and especially about 45% to about 50% by weight. 10. The photopolymerization initiator (III) comprises from about 0.01% to about 2% by weight of the total photopolymerizable acrylic component of the composition.
0% by weight, preferably about 0.1% to about 10% by weight, more preferably about 0.1% to about 5% by weight,
A composition according to claim 1 and most preferably present in a concentration from about 1% to about 5% by weight. 11. Use of the composition according to claim 1 for bonding a data-carrying material, such as polycarbonate, to a protective or covering material. 12. A data-carrying laminate comprising at least one data-carrying substrate bonded to another substrate selected from a data-carrying substrate and a transparent protective material by the adhesive composition according to claim 1. Wherein the adhesive composition is photocured between the data-carrying substrate (s) and in contact with the data-carrying substrate (s) and / or the protective substrate. laminate. 13. The data-carrying substrate is of the following group: polymers of monoolefins and diolefins; polyolefins; copolymers of monoolefins and diolefins; hydrocarbon resins; polystyrene and the like; styrene and dienes or acrylic derivatives. Copolymers with styrene; graft polymers of styrene; halogen-containing polymers; polymers derived from α, β-unsaturated acids and their derivatives; polymers derived from unsaturated alcohols and amines; homopolymers and copolymers of cyclic ethers; Polyethylene oxides and sulfides; Polyurethanes; Polyamides and copolyamides derived from diamines and dicarboxylic acids; Polyureas, Polyimides, Polyamide-imides, Polyetherimides, Polyesterimides; Polyesters derived from dicarboxylic acids and diols; polybenzimidazoles;
Using polycarbonates and polyester carbonates; polysulfones, polyethersulfones and polyetherketones; crosslinked polymers derived from aldehydes; dry and non-dry alkyd resins; unsaturated polyester resins; crosslinkable acrylic resins derived from substituted acrylates; Crosslinked alkyd resins; Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or araliphatic glycidyl compounds; Natural polymers such as cellulose, rubber, gelatin and their chemically modified 13. The laminate of claim 12, wherein the laminate is selected from the group consisting of: a homologous derivative; a polymer blend; glass and mixtures thereof. 14. The data-carrying substrate comprises a polycarbonate material coated with a metal selected from gold, silver and aluminum, or a non-metal selected from silicon, silicon carbide, silicon nitride and mixtures thereof. 12. The laminate according to 12. 15. When bonded to a laminate according to claim 12, comprising: (I) measuring light emitted by the bonded adhesive composition at several points across the bonded surface. The method for detecting the thickness of the adhesive composition according to claim 1 at a specific point.